EP1273969B1 - Positive resist composition - Google Patents
Positive resist composition Download PDFInfo
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- EP1273969B1 EP1273969B1 EP02014079.4A EP02014079A EP1273969B1 EP 1273969 B1 EP1273969 B1 EP 1273969B1 EP 02014079 A EP02014079 A EP 02014079A EP 1273969 B1 EP1273969 B1 EP 1273969B1
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- substituent
- alkyl
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/108—Polyolefin or halogen containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/115—Cationic or anionic
Definitions
- the present invention relates to a positive resist composition preferably used in micro-lithographic processes for the manufacture of VLSI's and micro-tips with large capacities, and other photo-fabrication processes. More specifically, it relates to a positive resist composition capable of forming fine patterns with use of a vacuum ultraviolet ray having a wavelength not longer than 160 nm.
- Integrated circuits are still raising the degree of integration; in the manufacture of semiconductor tips such as VLSI's, it has become essential to process ultra-fine patterns comprising line widths below a quarter micron. As one of the means to reduce pattern dimension, it is well known to make short the wavelength of the exposure energy source used for resist pattern formation.
- the i line (365 nm) of a high-pressure mercury lamp has been used as the exposure source.
- positive resists for this light source a number of compositions based on a novolac resin and naphthoquinonediazide as a photo-sensitive material have been developed, which have achieved satisfactory results in the processing of lines having widths up to about 0.3 ⁇ m.
- the KrF excimer laser light (248 nm) instead of the i line has been adopted as the exposure light source.
- the use of the ArF excimer laser light (193 nm) and, further for the formation of patterns not exceeding 0.1 ⁇ m size, the use of the F 2 excimer laser light (157 nm) are under investigation.
- the ingredients composing resist materials and their chemical structures are also changing drastically. Since the conventional resist comprising a novolac resin and a naphthoquinonediazide compound exhibits a strong absorption in the deep UV region around 248 nm, the light is difficult to reach the bottom portion of the resist, thus the resist being of low sensitivity and giving patterns having a tapered configuration.
- the so-called chemical amplification resists have been developed in which a resin having a fundamental backbone of poly(hydroxystyrene) that exhibits a weak absorption in the 248 nm region and is protected by an acid-decomposable group is used as a principal ingredient, and in which a compound (photo acid generator) that generates an acid upon irradiation with a deep UV light is jointly used.
- the chemical amplification resist which changes the solubility in the developer via a decomposition reaction catalyzed by the acid generated at exposed areas, can form high-resolution patterns with a small amount of exposure.
- an improvement of chemical amplification resists is being investigated by replacing the acid-decomposable resin having a fundamental backbone of poly(hydroxystyrene) to another acid-decomposable resin in which an alicyclic structure not absorbing 193 nm light is introduced in the main or side chain of a polymer.
- Resists containing these fluoro-resins exhibited an insufficient dissolution contrast between the exposed and unexposed regions. Further, due to the specific water-repellent as well as oil-repellent property originating from the perfluoro structure, the improvement of the coating performance (the uniformity of the coating surface) and the suppression of development defect were also expected.
- R.R. Kunz et al. provide in Proc SPIE, volume 4345, pp. 285-295 (2001 ) a report on an experimental VUV absorbance study of fluorine-functionalized polystyrenes.
- a typical photoacid generator such as bis(t-butylphenyl) iodinium camphor sulfonate is added to terpolymers comprising 4-hexafluoroisopropanol styrene, t-butyl methacrylate and, as a third monomer e.g. (meth) acrylonitrile or a styrene containing a haloalkyl group to prepare a composition which is tested for the absorption properties.
- a typical photoacid generator such as bis(t-butylphenyl) iodinium camphor sulfonate is added to terpolymers comprising 4-hexafluoroisopropanol styrene, t-
- a first object of the invention is to provide a positive resist composition suitably used for exposure sources of 160 nm or shorter wavelength, in particular, the F 2 excimer laser (157 nm), and is more specifically to provide a positive resist composition exhibiting an improved surface roughness as well as an excellent storage stability. Further, it is to provide a positive resist composition with which development defect is reduced, too.
- a second object of the invention is to provide a positive resist composition suitably used for exposure sources of 160 nm or shorter wavelength, in particular, the F 2 excimer laser (157 nm), and is more specifically to provide a positive resist composition exhibiting an improved surface roughness as well as an improved scum performance.
- a third object of the invention is to provide a positive resist composition suitably used for exposure sources of 160 nm or shorter wavelength, in particular, the F 2 excimer laser (157 nm), and is more specifically to provide a positive resist composition exhibiting a sufficient transparency when a 157 nm light source is used, an excellent coating performance, suppressed development defect and a good dissolution contrast.
- the resin as component (A) for use in the invention comprises a repeating unit (1) represented by general formula (I) cited above, a repeating unit (2) represented by the general formula (II) in the appended Claim 1 that is copolymerizable with the unit represented by general formula (I) and has a function of increasing the solubility in an alkali developer via the decomposition caused by the action of acid, and a repeating unit (3) that is inactive to the action of acid and free of an alkali-soluble group, and decomposes by the action of acid to increase the solubility in an alkali developer.
- Repeating unit (1) is represented by general formula (I) as defined in the appended Claim 1
- repeating unit (2) that is copolymerizable with the unit represented by general formula (I) and has a function of increasing the solubility in an alkali developer via the decomposition caused by the action of acid, is represented by general formula (II) described in Claim 1.
- Repeating unit (3) should preferably contain a fluorine atom.
- alkyl group mentioned above one can mention, for example, those of straight chain or branched chain structure with 1 to 8 carbon atoms, and specificallymethyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl and octyl as preferable examples.
- the cycloalkyl group may be monocyclic or polycyclic; one can preferably mention, as monocyclic examples, those of 3 to 8 carbon atoms, i.e., for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
- the polycyclic examples preferably include those of 6 to 20 carbon atoms such as, for example, adamantyl, norbornyl, isobornyl, camphanyl, dicyclopentyl, ⁇ -pinel, tricyclodecanyl, tetracyclododecyl, androstanyl, etc.
- the cycloalkyl group includes those in which the carbon atoms constituting the ring are partially substituted with a hetero atom such as oxygen, sulfur, nitrogen, etc.
- the aryl groups are, for example, those with 6 to 15 carbon atoms, specifically including phenyl, tolyl, dimethylphenyl, 2,4,6-trimethylphenyl, naphthyl, anthryl, 9,10-dimethoxyanthryl, etc. as preferable examples.
- the aralkyl groups are, for example, those with 7 to 12 carbon atoms, specifically including benzyl, phenethyl, naphthylmethyl, etc. as preferable examples.
- alkenyl groups are, for example, those with 2 to 8 carbon atoms, specifically including vinyl, allyl, butenyl and cyclohexenyl as preferable examples.
- the alkoxyl groups are, for example, those with 1 to 8 carbon atoms, specifically including methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy, pentoxy, allyloxy, octoxy, etc. as preferable examples.
- acyl groups are, for example, those with 1 to 10 carbon atoms, specifically including formyl, acetyl, propanoyl, butanoyl, pivaloyl, octanoyl, benzoyl etc. as preferable examples.
- acyloxy groups are preferably, for example, those with 2 to 12 carbon atoms, specifically including acetoxy, propionyloxy, benzoyloxy, etc.
- the alkynyl groups are preferably, for example, those with 2 to 5 carbon atoms, specifically including ethynyl, propynyl, butynyl, etc.
- the alkoxycarbonyl groups include tertiary ones such as t-butoxycarbonyl, t-amyloxycarbonyl and 1-methyl-1-cyclohexyloxycarbonyl, etc.
- halogen atom As the halogen atom, one can mention fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
- alkylene group one can mention those with a straight chain or branched chain structure, including, for example, those with 1 to 8 carbon atoms such as methylene, ethylene, propylene, butylene, hexylene, octylene, etc.
- cycloalkylene group those with 5 to 8 carbon atoms such as cyclopentylene, cyclohexylene, etc. are mentioned.
- alkenylene group those with 2 to 6 carbon atoms are mentioned such as ethenylene, propenylene, butenylene, etc. all of which may preferably have a substituent.
- arylene group those with 6 to 15 carbon atoms are mentioned such as phenylene, tolylene, naphthylene, etc. all of which may preferably have a substituent.
- Substituents that these groups may have include those having an active hydrogen such as an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, etc., a halogen (F, Cl, Brand I) atom, an alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.) group, a thioether group, an acyl (acetyl, propanoyl, benzoyl, etc.) group, an acyloxy (acetoxy, propanoyloxy, benzoyloxy, etc.) group, an alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc.) group, an alkyl (methyl, ethyl, propyl and butyl) group, a cycloalkyl (cyclohexyl) group, an aryl (phenyl) group, a
- At least one of R 5 in general formula (I), R 1 in general formula (II), and R 17 in general formula (III) is preferably a trifluoromethyl group.
- the group that is contained in the resin (A) of the invention and decomposed by the action of acid to exhibit alkali-solubility includes, for example, -O-C(R 18d )(R 18e )(R 18f ), -O-C(R 18d )(R 18e )(OR 18f ), -O-COO-C(R 18d )(R 18e )(R 18f ), -O-C(R 01 )(R 02 )COO-C(R 18d )(R 18e )(R 18f ), -COO-C(R 18d )(R 18e )(R 18f ), -COO-C(R 18d )(R 18e )(OR 18f ), etc.
- R 18d to R 18f which may be the same or different, each represent an alkyl, a cycloalkyl, an alkenyl, an aralkyl or an aryl group, each of which may have a substituent; and two of R 18d to R 18f may connect together to form a ring.
- the ring resulting from the connection of two of R 18d to R 18f 3-to 8-membered ones are, for example, mentioned.
- cyclic groups include cyclopropane, cyclopentane, cyclohexane, tetramethylene oxide, pentamethylene oxide, hexamethylene oxide, furan, pyran, dioxonol, 1,3-dioxolane, etc.
- R 01 and R 02 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group all of which may be substituted with one of the substituents enumerated above.
- Preferable examples include the ether or ester group of a tertiary alkyl group such as t-butyl, t-amyl, 1-alkyl-1-cyclohexyl, 2-alkyl-2-adamantyl, 2-adamantyl-2-propyl, 2-(4-methylcyclohexyl)-2-propyl, etc., the acetal or acetal ester group of 1-alkoxy-1-ethoxy, tetrahydropyranyl, etc., a t-alkylcarbonate group, a t-alkylcarbonylmethoxy group, etc. More preferable examples are the acetal groups of a 1-alkoxy-1-ethoxy group a tetrahydropyranyl group, etc.
- the resin is actively decomposed by acid. Accordingly, due to the expanded range of selection for the acid-generating compound to be jointly used, the resin is advantageous as regard to sensitivity enhancement, the property shift occurring in the period between exposure and post-baking, etc.
- Particularly preferable acetal groups are those containing the alkoxy group derived from the aforementioned perfluoroalkyl group as the 1-alkoxy component of the acetal. With such a compound, the transmittance of short wavelength rays (for example, the 157 nm light from an F 2 excimer laser) can be further raised.
- repeating unit (1) As specific examples of the repeating unit (1), the following ones are mentioned, but the scope of the invention is not limited by them.
- repeating unit (2) represented by general formula (II) are shown below, but the scope of the invention is not limited by them.
- Repeating unit (3) is one that is inactive to the action of acid and free of any alkali-soluble group; this unit has no such a group that is decomposed by acid to exhibit alkali-solubility as was explained hereinabove.
- To be inactive to the action of acid means that no chemical reaction results by the action of acid.
- This repeating unit is preferably selected from the group consisting of (meth) acrylic acid esters, (meth)acrylonitrile, and styrene that may contain an alkyl, alkoxy, acyloxy or haloalkyl group, or a chlorine, bromide or iodine atom as a substituent.
- alkali-soluble group that repeating unit (3) does not contain, those, for example, having a pKa value not exceeding 11 are mentioned such as a phenolic hydroxide group, active methylene group, imide group, carboxyl group, sulfonic acid group, sulfinic acid group, etc.
- the monomer usable as repeating unit (3) includes, for example, those shown below. That is, such examples are compounds having one addition-polymerizable unsaturated bond chosen from, for example, acrylic acid esters, acrylamide derivatives, methacrylic acid esters, methacrylamide derivatives, allyl compounds, vinyl ethers, vinyl esters, styrene derivatives, crotonic acid esters, etc. except those defined above.
- Acrylic acid esters such as, for example, alkyl (the number of the carbon atoms in the alkyl group being preferably 1 to 10) acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) and aryl acrylates (for example, phenyl acrylate, etc.); methacrylic acid esters such as, for example, alkyl (
- Repeating unit (3) is inactive to the action of acid, free of any alkali-soluble group, and preferably contains at least one fluorine atom.
- repeating unit (3) one can mention ⁇ -trifluoroacrylic acid esters, the fluorine-containing alkyl esters of (meth)acrylic acid, the benzenesulfonic acid esters of vinyl phenol that contain a fluorine atom or a fluorine-substituted alkyl group (exemplified by trifluoromethyl group) as substituent, and the repeating units represented by the general formula (IV') as defined in the appended Claim 4.
- the ester moiety of ⁇ -trifluoroacrylic acid esters consists of an alkyl group that contains preferably 1 to 20 carbon atoms and is of straight chain, branched chain or cyclic structure. But more preferably, the ester moiety consists of a straight chain, branched chain, or cyclic alkyl group containing 1 to 10 carbon atoms or a cyclic alkyl group containing 6 to 14 carbon atoms.
- the ester moiety of the fluorine-containing alkyl ester of (meth)acrylic acid consists of an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom and which is of straight chain, branched chain or cyclic structure with 1 to 20 carbon atoms. More preferably, the ester moiety is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom and which is of straight chain, branched chain or cyclic structure with 1 to 10 carbon atoms, or a cyclic alkyl group of 6 to 14 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.
- the number of the fluorine atoms usually lies in the range of from 1 to 38, and preferably from 2 to 19.
- the fluorine-containing alkyl group those that have no fluorine atom on the carbon atom bonded to the ester group are preferred.
- R 5 , R 6 , R 7 and R 50 to R 55 in formula (IV') are the same as those of the corresponding groups in formula (I).
- R 60 represents an alkyl group, an alkylcarbonyl group, a monocyclic or polycyclic cycloalkyl group, a monocyclic or polycyclic cycloalkylcarbonyl group, an alkenyl group, an alkenylcarbonyl group, an aralkyl group, an aralkylcarbonyl group, an aryl group or an arylcarbonyl group.
- R 60 represents an alkyl group, an alkylcarbonyl group, a monocyclic or polycyclic cycloalkyl group, a monocyclic or polycyclic cycloalkylcarbonyl group, an alkenyl group, an alkenylcarbonyl group, an aralkyl group, an aralkylcarbonyl group, an aryl group or an arylcarbonyl group.
- R 60 those in which at least one hydrogen atom is substituted with a fluorine atom are preferred.
- the content of the repeating unit (1) represented by general formula (I) is usually 30 to 85 mol%, preferably 40 to 80 mol%, and still more preferably 50 to 70 mol% in resin (A).
- the content of the repeating unit (2) is usually 10 to 50 mol%, preferably 20 to 40 mol%, and still more preferably 25 to 35 mol% in resin (A).
- the content of the repeating unit (3) is usually 2 to 40 mol%, preferably 3 to 30 mol%, and still more preferably 5 to 20 mol% in resin (A).
- Resin (A) of the invention can contain, in addition to the repeating units cited above, another polymerizable monomer as a copolymerization component for the purpose of further improving various properties of the positive-type resist of the invention.
- Each repeating structural unit shown by the specific examples enumerated hereinabove may consist of single species or plural species used as mixtures.
- a preferable range of the molecular weight of resin (A) of the invention comprising the repeating units enumerated hereinabove is from 1, 000 to 200, 000, and more preferably from 3, 000 to 20,000 in terms of weight-average value for practical use.
- the molecular weight distribution lies in the range of 1 to 10, preferably 1 to 3, and more preferably 1 to 2 for practical use.
- Resins having a narrower molecular weight distribution excel in resolution, give rise to smooth resist configuration with smoother side walls of the resist pattern, and excel in the roughness characateristics.
- resin (A) of the invention is used at a content of 50 to 99.5% by weight, preferably 60 to 98% by weight, and more preferably 65 to 95% by weight.
- resin (A') that contains the above-cited repeating units (1) and (2) and decomposes by the action of acid to enhance the solubility in an alkali developer from the viewpoint of development defect reduction.
- the molecular weight of resin (A') is substantially the same as that of resin (A).
- Resin (A') is usually used in a content of from 2 to 30 % by weight, preferably 5 to 20% by weight, and more preferably 10 to 15% by weight relative to resin (A).
- the compound which generates an acid upon irradiation with one of an actinic ray and a radiation can be suitably selected from photo-initiators for cationic photo-polymerization, photo-initiators for radical photo-polymerization, photodecolouring agents for dyes, photodiscolouring agents and compounds which generate an acid upon irradiation with the known kinds of light now in practical use for in micro-resist fabrication etc., (including UV light of 400 to 200 nm wavelength, deep UV light, particularly preferably the g-line, h-line and i-line and KrF excimer laser light), the ArF excimer laser light, the F 2 excimer laser light, electron beam, X-ray, molecular beam or ion beam. Further, mixtures of these compounds may also be appropriately used.
- Still other compounds that generate an acid upon irradiation with one of an actinic ray and a radiation include the onium salts such as the diazonium salts described in, for example, S. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974 ), T. S. Bal et al, Polymer, 21, 423 (1980 ), etc., the ammonium salts described in US Patent Nos. 4,069,055 , 4,069,056 , and Re 27,992 , Japanese Patent Laid-Open No. 140140/1991 , etc., the phosphonium salts described in D. C. Necker et al., Macromolecules, 17, 2468 (1984 ), C. S.
- onium salts such as the diazonium salts described in, for example, S. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974 ), T. S. Bal et al, Polymer, 21, 423 (1980 ), etc., the
- R 201 is a substituted or unsubstituted aryl or alkenyl group
- R 202 is a substituted or unsubstituted aryl, alkenyl or alkyl group, or -CY 3 , where Y is a chlorine or bromine atom.
- Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aryl group.
- substituents one can mention an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.
- R 203 , R 204 , and R 205 each independently represent a substituted or unsubstituted alkyl or aryl group, and preferably an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms or a substituted derivative of the two.
- Preferable substituents for the aryl group include an alkoxy group of 1 to 8 carbon atoms, an alkyl group of 1 to 8 carbon atoms, a cycloalkyl group, a nitro group, a carboxyl group, a mercapto group, a hydroxy group and a halogen atom.
- preferred substituents for the alkyl group include an alkoxy, carboxyl or alkoxycarbonyl group of 1 to 8 carbon atoms.
- Z - represents an anion, specifically including the anions of an alkylsulfonic acid, cycloalkylsulfonic acid, perfluoroalkylsulfonic acid each of which may have a substituent, an arylsulfonic acid (exemplified by benzenesulfonic acid, naphthalenesulfonic acid and anthracenesulfonic acid each of which may have a substituent).
- R 203 , R 204 and R 205 may connect together via a single bond thereof or a substituent.
- Ar 1 and Ar 2 may connect together via a single bond thereof or a substituent.
- Typical examples include the following compounds, to which preferable compounds are not restricted.
- onium salts represented by general formulae (PAG3) and (PAG4) are known in the art and can be synthesized, for example, by the methods described in J. W. Knapczyk et al., J. Am. Chem. Soc., 91, 145 (1969 ), A. L. Maycok et al., J. Org. Chem., 35, 2532, (1970 ), E. Goethas et al., Bull. Soc. Chem. Belg., 73, 546, (1964 ), H. M. Leicester, J. Am. Chem. Soc., 51, 3587 (1929 ), J. V. Crivello et al., J. Polym. Chem. Ed., 18, 2677 (1980 ), US Patent Nos. 2,807,648 and 4,247,473 , Japanese Patent Laid-Open No. 101331/1978 , etc.
- Ar 3 and Ar 4 each independently represent a substituted or unsubstituted aryl group
- R 206 represents a substituted or unsubstitutedalkyl or aryl group
- A represents a substituted or unsubstituted alkylene, alkenylene or arylene group.
- Typical examples include those cited below, to which, however, preferable compounds are not restricted.
- R represents an alkyl group of straight chain, branched chain or cyclic structure, or an aryl group that may be substituted.
- R 207 represents a substituted or unsubstituted alkyl, cycloalkyl, aryl or aralkyl group
- R 208 and R 209 each represent a substituted or unsubstituted alkyl, cycloalkyl, aryl, aralkyl, cyano or acyl group
- R 208 and R 209 may combine together to form a carbocyclic ring or a heterocycylic ring including an oxygen, nitrogen or sulfur atom.
- photo-acid generators those represented by formulae (PAG3) to (PAG8) and capable of generating an organic sulfonic acid are preferred.
- photo-acid generators that generate either a benzenesulfonic acid having a fluorine atom or a fluorine-substituted alkyl group as a substituent or a fluorine-containing alkylsulfonic acid are preferred.
- Nonaflate, pentafluorobenzenesulfonate and 3,5-bis(trifluoromethyl)benzenesulfonate are still more preferred.
- the added amount of the compound in (B) of the invention that generates an acid upon irradiation with one of an actinic ray or a radiation usually lies in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably 1 to 7% by weight based on the total solid content of the composition of the invention.
- These compounds may be used individually or in combination of two or more thereof.
- composition of the invention is dissolved in a solvent which can dissolve each ingredient cited above and coated on a substrate.
- solvents used for such purpose include 1-methoxy-2-propanol acetate, 1-methoxy-2-propanol, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, ⁇ -butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropinonate, ethyl ethoxypropionate, methyl pyruvate, eth
- the amount of the components other than the solvent is usually 3 to 30wt%, preferably 5 to 25wt% based on content of the solvent.
- the positive resist composition of the invention can be incorporated with a surfactant containing at least one of a group consisting of a fluorine atom and a silicon atom. More specifically, the positive resist composition of the invention can contain one or more compounds selected from the group consisting of fluorine-containing surfactants, silicone-based surfactants and those containing both of fluorine and silicon atoms. The incorporation of the surfactant containing at least one of a group consisting of a fluorine atom and a silicon atom acts to effectively suppress the generation of development defect and improve coating performance.
- fluorine-containing or silicone-based surfactants such as, for example, Eftop EF301, EF303 and EF352 (all manufactured by Shin-Akita Kasei K. K.), Florad FC430 and 431 (both manufactured by Sumitomo 3M, Inc.), Megafac F171, F173, F176, F189 and R08 (all manufactured by Dainippon Ink and Chemicals, Inc.), Asahi-GardAG710, Surflon S-382, SC101, 102, 103, 104, 105 and 106, (all manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Industries, Inc.), etc.
- a polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.
- a silicon-based surfactant can also be used as a silicon-based surfactant.
- the incorporated amount of the surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight on the basis of the solid content in the composition of the invention.
- These surfactants may be used individually or in combination of two or more thereof.
- the composition of the invention is preferably incorporated with an acid diffusion-suppressing agent in order to prevent the performance shift caused not only by the time elapsed after the irradiation with an actinic ray or a radiation till post-baking (T-top shape formation, sensitivity fluctuation; patterned line width fluctuation, etc.), but also by the time elapse after coating, and further to suppress an excessive diffusion of acid during post-baking (which leads to the deterioration of pattern resolution).
- the acid diffusion-suppressing agent usually comprises an organic basic compound such as, for example, those containing a basic nitrogen, and a compound whose conjugated acid has a pKa value not less than 4 is preferably used.
- R 250 , R 251 and R 252 which may be the same or different, each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
- R 251 and R 252 may connect together to form a ring.
- R 253 , R 254 , R 255 and R 256 which may be the same or different, each represent an alkyl group having 1 to 6 carbon atoms.
- More preferable compounds are nitrogen-containing basic compounds having two or more nitrogen atoms each lying in different chemical environments within a single molecule.
- Particularly preferable compounds are those containing both of a substituted or unsubstituted amino group and a cyclic structure including a nitrogen atom, or those containing an alkylamino group.
- preferable compounds include substituted or unsubstituted guanidines, substituted or unsubstituted aminopyridines, substituted or unsubstituted aminoalkylpyridines, substituted or unsubstituted aminopyrrolidines, substituted or unsubstituted indazoles, imidazole, substituted or unsubstituted pyrazoles, substituted or unsubstituted pyrazines, substituted or unsubstituted pyrimidines,substituted or unsubstituted purines,substituted or unsubstituted imidazolines, substituted or unsubstituted pyrazolines, substituted or unsubstituted piperazines, substituted or unsubstituted aminomorpholines, substituted or unsubstituted aminoalkylmorpholine, etc.
- Preferable substituents include an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxy group, a cyano group, etc.
- Particularly preferable compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperadine, N-(2-aminoethyl)piperadine, N-(2-aminoeth
- nitrogen-containing basic compounds can be used individually or in combination of two or more thereof.
- the use ratio of the acid-generating agent and the organic basic compound in the composition should preferably lie in the range of 2.5 to 300 in the molar ratio of (acid-generating agent) / (organic basic compound). In the case where this molar ratio is below 2.5, the sensitivity becomes low and the pattern resolution sometimes deteriorates; while, with a molar ratio over 300, not only resist patterns tend to fatten, resulting in resolution deterioration when the time after exposure till post-baking elapses too long, but also the pattern resolution sometimes deteriorates.
- the molar ratio of (acid-generator)/(organic basic compound) is preferably 5.0 to 200, and more preferably 7.0 to 150.
- pattern formation in a resist film is performed by first coating the positive resist composition of the invention on a substrate (examples: a transparent substrate such as a silicon/silicon dioxide film, a glass substrate, an ITO plate, etc.), then conducting irradiation of the coating by means of an actinic light or radiation exposing apparatus, and thereafter conducting post-baking, developing, rinsing and drying. Via these procedures, a good-quality resist pattern can be formed.
- a substrate examples: a transparent substrate such as a silicon/silicon dioxide film, a glass substrate, an ITO plate, etc.
- an aqueous solution of an alkali compound including inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, etc., and organic ones such as primary amines exemplified by ethylamine, n-propylamine, etc.
- aqueous alkali solution enumerated above can further contain an alcohol such as isopropyl alcohol, etc. and a surfactant such as nonionic one each at an appropriate amount.
- quaternary ammonium salts are preferred, and tetramethylammonium hydroxide and choline are still more preferred.
- Table 1 Resin (A) Structure Molecular Weight P-1 15000 P-2 23000 P-3 29000 P-4 26000 P-5 27000 P-6 37000 P-7 19000 P-8* 30000 P-9 25000 P-10 21000 P-11* 10000 P-12 19000 B-1 16000 B-2 21000 B-3 23000 C-1 17000 *For reference and not within the scope of resing (A)
- Example 13 a resist composition was prepared in a similar manner as in Example 1 except that, instead of 1.36 g of (P-1), 1.2 g of (P-1) and 0.16 g of a complementary resin (B-1) were used.
- a resist composition was prepared in a similar manner as in (Reference) Example 8 except that instead of 1.36 g of (P-8), 1.2 g of (P-8) and 0.16 g of a complementary resin (B-1) were used.
- Example 15 a resist composition was prepared in a similar manner as in Example 5 except that instead of 1.36 g of (P-5), 1.2 g of (P-5) and 0.16 g of a complementary resin (B-3) were used.
- Comparative Example 1 a resist composition was prepared in a similar manner as in Example 1 except that the resin was changed to (C-1) shown in Table 1.
- each resist solution prepared above was coated, with use of a spin coater, on a silicon wafer that had been subjected to a hexamethyldisilazane treatment, and dried on a vacuum contact type-hot plate kept at 110°C for 90 sec to give a 0.3 ⁇ m thick resist film.
- the resist film thus obtained was subjected to an image exposure with a KrF excimer stepper (FPA-3000EX5, a product of Canon, Inc.), followedbypost-baking at 110°C for 90 sec. Thereafter, the resist film was developed with a 0.262 N TMAH aqueous solution to give a L/S pattern of 0.15 ⁇ m rule.
- the: particle increment was calculated by (Particle Number After Time Passage) - (Initial Particle Number) for evaluation.
- the number of particles with a size of 0.3 ⁇ m or larger present in one ml of the resist composition solution was counted.
- Number of Development Defect For each resist pattern prepared according to the procedures described above, the number of development defect was measured with use of a KLA-2112 inspector manufactured by KLA-Tencor Corp. The primary data obtained was regarded as the number of development defect.
- the particle number in the resist fluid is desirably small immediately after preparation as well as after storage, and the surface roughness was excellent.
- each resist solution prepared above was coated, with use of a spin coater, on a silicon wafer that had been subjected to a hexamethyldisilazane treatment, and dried on a vacuum contact type-hot plate kept at 110°C for 90 sec to give a 0.3 ⁇ m thick resist film.
- the coated film was subjected to an image exposure with a KrF excimer stepper (FPA-3000EX5, a product of Canon, Inc.). Then, after post-baked at 110°C for 90 sec, the resist film was developed with a 0. 262 N TMAH aqueous solution to give a L/S pattern of 0.13 ⁇ m rule.
- the resist compositions comprising a fluorine atom-containing resin according to the invention are preferable giving little surface roughness and scum.
- each sample solution was coated on a calcium fluoride disk with use of a spin coater, and dried at 120°C for 5 min to give a 0.1 ⁇ m thick resist film.
- the absorption of the coated film was measured with an Acton CAMS-507 spectrometer, and the transmittance at 157 nm was calculated. The results are shown in Table 5.
- the surfactant used in each sample prepared for transmittance measurement described above was changed to the following surfactants, W-1 to W-4, to prepare resist compositions of the invention.
- the surfactants used are shown in Table 6.
- Each code represents the following surfactants.
- W1 Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine-containing type)
- W2 Megafac R08 (made by Dainippon Ink and Chemicals, Inc.) (fluorine-containing and silicon-based)
- W3 Polysiloxane polymer KR-341 (made by Shin-Etsu Chemical Co., Ltd.)
- W4 Polyoxyethylene nonyl phenyl ether
- each resist solution was coated, with use of a spin coater, on a silicon wafer that had been subjected to a hexamethyldisilazane treatment, and dried on a vacuum contact type-hot plate kept at 110°C for 90 sec to give a 0.3 ⁇ m thick resist film.
- the coated film was subjected to an image exposure with a KrF excimer stepper (FPA-3000EX5, a product of Canon, Inc.). Then, after post-baked at 110°C for 90 sec, the resist film was developed with a 0.262 N TMAH aqueous solution to give a L/S pattern of 0.15 ⁇ m rule.
- Each resist solution was coated on an 8-inch silicon wafer. Then, the same procedures for the preparation of the resist coating as described above were conducted to give a coated resist film for the measurement of the uniformity over the entire coated plane.
- the thickness of the coating was measured at 36 points evenly distributed along two wafer diameter directions running crosswise. The standard deviation of all the measured values was calculated. The samples in which the threefold of the standard deviation did not exceed 50 were evaluated as O, those in which the value was 50 or larger were evaluated as X.
- Table 6 Resin (A) of the Invention Surfactant Used Development Defect Coating Performance P-41 W1 30 O P-42 W2 24 O P-43 W3 20 O P-44 W2 36 O P-45 W2 30 O P-46 W3 24 O P-47 W1 22 O P-48 W2 30 O P-49 W3 30 O P-50 W2 28 O P-51 W1 40 O P-52 W3 36 O P-53 W3 35 O P-54 W3 32 O P-55 W1 38 O P-56 W2 48 O P-57 W1 46 O P-58 W1 48 O P-41 None 2000 X P-41 W4 650 X
- composition of the invention that is incorporated with a surfactant containing at least one of a group consisting of a fluorine atom and a silicon atom is superior, compared to Comparative Examples in which no such surfactant is incorporated, as for coating performance and gives rise to far fewer development defects.
- resist solutions were prepared in the same way as in the term of [Measurement of Transmittance]. After filtered through a Teflon filter of 0.1 ⁇ m aperture size, each resist solution prepared above was coated on a silicon wafer that had been subjected to a hexamethyldisilazane treatment with use of a spin coater, and dried on a vacuum contact type-hot plate kept at 110°C for 90 sec to give a 0.1 ⁇ m thick resist film.
- VUVES-4500 manufactured by Lithotec Japan Corp. was used for each of the resulting resist films to measure the dissolution contrast between the exposed and unexposed regions for 157 nm irradiation.
- compositions of the invention exhibit a dissolution contrast equivalent to that of the resist of the comparative example that is practically used for the KrF excimer laser, and thus have an equivalent image forming capability.
- a positive resist composition of the invention With use of a positive resist composition of the invention, one can further provide a positive resist composition with which surface roughness and storage stability are improved along with reduced development defect.
- the positive resist composition of the invention can provide a positive resist composition that exhibits a sufficient transparency and a desirable image forming capability at a wavelength region as short as 157 nm, and that improves the coating performance and the development defect problem both of which are deteriorated by the use of a fluorine-containing resin.
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Description
- The present invention relates to a positive resist composition preferably used in micro-lithographic processes for the manufacture of VLSI's and micro-tips with large capacities, and other photo-fabrication processes. More specifically, it relates to a positive resist composition capable of forming fine patterns with use of a vacuum ultraviolet ray having a wavelength not longer than 160 nm.
- Integrated circuits are still raising the degree of integration; in the manufacture of semiconductor tips such as VLSI's, it has become essential to process ultra-fine patterns comprising line widths below a quarter micron. As one of the means to reduce pattern dimension, it is well known to make short the wavelength of the exposure energy source used for resist pattern formation.
- As an example, in the manufacture of semiconductor tips having a degree of integration up to 64 Mbits, the i line (365 nm) of a high-pressure mercury lamp has been used as the exposure source. As positive resists for this light source, a number of compositions based on a novolac resin and naphthoquinonediazide as a photo-sensitive material have been developed, which have achieved satisfactory results in the processing of lines having widths up to about 0.3 µm. Further, in the manufacture of semiconductor tips having a degree of integration of 256 Mega bits or higher, the KrF excimer laser light (248 nm) instead of the i line has been adopted as the exposure light source.
- Further, in order to cope with the manufacture of semiconductors with a degree of integration of 1 Giga bits or higher, the use of the ArF excimer laser light (193 nm) and, further for the formation of patterns not exceeding 0.1 µm size, the use of the F2 excimer laser light (157 nm) are under investigation.
- To adapt themselves to the wavelength shortening in the light source, the ingredients composing resist materials and their chemical structures are also changing drastically. Since the conventional resist comprising a novolac resin and a naphthoquinonediazide compound exhibits a strong absorption in the deep UV region around 248 nm, the light is difficult to reach the bottom portion of the resist, thus the resist being of low sensitivity and giving patterns having a tapered configuration.
- To solve such problems, the so-called chemical amplification resists have been developed in which a resin having a fundamental backbone of poly(hydroxystyrene) that exhibits a weak absorption in the 248 nm region and is protected by an acid-decomposable group is used as a principal ingredient, and in which a compound (photo acid generator) that generates an acid upon irradiation with a deep UV light is jointly used. The chemical amplification resist, which changes the solubility in the developer via a decomposition reaction catalyzed by the acid generated at exposed areas, can form high-resolution patterns with a small amount of exposure.
- However, in the case of using an ArF excimer laser light (193 nm), a satisfactory performance was not achieved even with the chemical amplification resist since compounds having an aromatic group essentially exhibit a strong absorption at the 193 nm wavelength region.
- To solve this problem, an improvement of chemical amplification resists is being investigated by replacing the acid-decomposable resin having a fundamental backbone of poly(hydroxystyrene) to another acid-decomposable resin in which an alicyclic structure not absorbing 193 nm light is introduced in the main or side chain of a polymer.
- For the F2 excimer laser light (157 nm), however, even the above-cited alicyclic resins proved to have a strong absorption in the 157 nm region, thus being unsatisfactory to form 0.1 µm or finer patterns. In contrast, it has been reported in Proc. SPIE, Vol. 3678, p.13 (1999) that resins to which fluorine atoms are introduced in the form of perfluoro structure exhibit a sufficient transparency for the 157 nm radiation. Further, effective structures of such fluorine-containing resins have been proposed inProc. SPIE, Vol. 3999, p.330 (2000), p.357 (2000) and p.365 (2000),
WO-00/17712 - At SPIE's Micro-lithography Symposium 2001, a resist for the F2 light using a copolymer of 4-[bis(trifluoromethyl)-hydroxymethyl]styrene with t-butyl methacrylate was reported. But the resist based on this copolymer had a problem that the roughness of the pattern surface after development is too large. Moreover, the number of particles in the resist fluid was large, which further increased with the expansion of storage period thus causing a problem in storage stability.
- In addition to these problems, there was still another problem that a large amount of scum generated in the space portions in line-and-space patterns. In the specification of
DE10054996A is disclosed a resin for F2 resists obtained by copolymerizing an acrylate monomer having a fluorine atom at the α-position or in the ester moiety with p-hydroxystyrene or a tertiary ester-containing (meth) acrylate. However, this type of resist also suffered from the problem of noticeable scum generation in the space portion in line-and-space patterns. - Resists containing these fluoro-resins exhibited an insufficient dissolution contrast between the exposed and unexposed regions. Further, due to the specific water-repellent as well as oil-repellent property originating from the perfluoro structure, the improvement of the coating performance (the uniformity of the coating surface) and the suppression of development defect were also expected.
- R.R. Kunz et al. provide in Proc SPIE, volume 4345, pp. 285-295 (2001) a report on an experimental VUV absorbance study of fluorine-functionalized polystyrenes. Specifically, a typical photoacid generator such as bis(t-butylphenyl) iodinium camphor sulfonate is added to terpolymers comprising 4-hexafluoroisopropanol styrene, t-butyl methacrylate and, as a third monomer e.g. (meth) acrylonitrile or a styrene containing a haloalkyl group to prepare a composition which is tested for the absorption properties.
- Accordingly, a first object of the invention is to provide a positive resist composition suitably used for exposure sources of 160 nm or shorter wavelength, in particular, the F2 excimer laser (157 nm), and is more specifically to provide a positive resist composition exhibiting an improved surface roughness as well as an excellent storage stability. Further, it is to provide a positive resist composition with which development defect is reduced, too.
- A second object of the invention is to provide a positive resist composition suitably used for exposure sources of 160 nm or shorter wavelength, in particular, the F2 excimer laser (157 nm), and is more specifically to provide a positive resist composition exhibiting an improved surface roughness as well as an improved scum performance.
- A third object of the invention is to provide a positive resist composition suitably used for exposure sources of 160 nm or shorter wavelength, in particular, the F2 excimer laser (157 nm), and is more specifically to provide a positive resist composition exhibiting a sufficient transparency when a 157 nm light source is used, an excellent coating performance, suppressed development defect and a good dissolution contrast.
- In view of the various characteristics mentioned above, the present inventors have devised the invention as a result of a focused investigation by finding that the objects of the invention can be completely achieved with use of specific positive resist compositions as defined in the appended claims.
- In the following, compounds used for the invention will be described in detail.
- The resin as component (A) for use in the invention comprises a repeating unit (1) represented by general formula (I) cited above, a repeating unit (2) represented by the general formula (II) in the appended Claim 1 that is copolymerizable with the unit represented by general formula (I) and has a function of increasing the solubility in an alkali developer via the decomposition caused by the action of acid, and a repeating unit (3) that is inactive to the action of acid and free of an alkali-soluble group, and decomposes by the action of acid to increase the solubility in an alkali developer.
- Repeating unit (1) is represented by general formula (I) as defined in the appended Claim 1, and repeating unit (2), that is copolymerizable with the unit represented by general formula (I) and has a function of increasing the solubility in an alkali developer via the decomposition caused by the action of acid, is represented by general formula (II) described in Claim 1.
- Repeating unit (3) should preferably contain a fluorine atom.
- As the alkyl group mentioned above, one can mention, for example, those of straight chain or branched chain structure with 1 to 8 carbon atoms, and specificallymethyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl and octyl as preferable examples.
- The cycloalkyl group may be monocyclic or polycyclic; one can preferably mention, as monocyclic examples, those of 3 to 8 carbon atoms, i.e., for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The polycyclic examples preferably include those of 6 to 20 carbon atoms such as, for example, adamantyl, norbornyl, isobornyl, camphanyl, dicyclopentyl, α-pinel, tricyclodecanyl, tetracyclododecyl, androstanyl, etc. The cycloalkyl group includes those in which the carbon atoms constituting the ring are partially substituted with a hetero atom such as oxygen, sulfur, nitrogen, etc.
- The aryl groups are, for example, those with 6 to 15 carbon atoms, specifically including phenyl, tolyl, dimethylphenyl, 2,4,6-trimethylphenyl, naphthyl, anthryl, 9,10-dimethoxyanthryl, etc. as preferable examples.
- The aralkyl groups are, for example, those with 7 to 12 carbon atoms, specifically including benzyl, phenethyl, naphthylmethyl, etc. as preferable examples.
- The alkenyl groups are, for example, those with 2 to 8 carbon atoms, specifically including vinyl, allyl, butenyl and cyclohexenyl as preferable examples.
- The alkoxyl groups are, for example, those with 1 to 8 carbon atoms, specifically including methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy, pentoxy, allyloxy, octoxy, etc. as preferable examples.
- The acyl groups are, for example, those with 1 to 10 carbon atoms, specifically including formyl, acetyl, propanoyl, butanoyl, pivaloyl, octanoyl, benzoyl etc. as preferable examples.
- The acyloxy groups are preferably, for example, those with 2 to 12 carbon atoms, specifically including acetoxy, propionyloxy, benzoyloxy, etc.
- The alkynyl groups are preferably, for example, those with 2 to 5 carbon atoms, specifically including ethynyl, propynyl, butynyl, etc.
- The alkoxycarbonyl groups include tertiary ones such as t-butoxycarbonyl, t-amyloxycarbonyl and 1-methyl-1-cyclohexyloxycarbonyl, etc.
- As the halogen atom, one can mention fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
- As the alkylene group, one can mention those with a straight chain or branched chain structure, including, for example, those with 1 to 8 carbon atoms such as methylene, ethylene, propylene, butylene, hexylene, octylene, etc.
- As the cycloalkylene group, those with 5 to 8 carbon atoms such as cyclopentylene, cyclohexylene, etc. are mentioned.
- As the alkenylene group, those with 2 to 6 carbon atoms are mentioned such as ethenylene, propenylene, butenylene, etc. all of which may preferably have a substituent.
- As the arylene group, those with 6 to 15 carbon atoms are mentioned such as phenylene, tolylene, naphthylene, etc. all of which may preferably have a substituent.
- The alkyl group, cycloalkyl group, alkoxy group, acyl group, acyloxy group, alkynyl group, alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group, alkylene group, cycloalkylene group, alkenylene group, arylene group, etc. described heretofore each may have a substituent.
- Substituents that these groups may have include those having an active hydrogen such as an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, etc., a halogen (F, Cl, Brand I) atom, an alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.) group, a thioether group, an acyl (acetyl, propanoyl, benzoyl, etc.) group, an acyloxy (acetoxy, propanoyloxy, benzoyloxy, etc.) group, an alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc.) group, an alkyl (methyl, ethyl, propyl and butyl) group, a cycloalkyl (cyclohexyl) group, an aryl (phenyl) group, a cyano group, nitro group, etc.
- In the invention, at least one of R5 in general formula (I), R1 in general formula (II), and R17 in general formula (III) is preferably a trifluoromethyl group.
- The group that is contained in the resin (A) of the invention and decomposed by the action of acid to exhibit alkali-solubility includes, for example, -O-C(R18d)(R18e)(R18f), -O-C(R18d)(R18e)(OR18f), -O-COO-C(R18d)(R18e)(R18f), -O-C(R01)(R02)COO-C(R18d)(R18e)(R18f), -COO-C(R18d)(R18e)(R18f), -COO-C(R18d)(R18e)(OR18f), etc. R18d to R18f, which may be the same or different, each represent an alkyl, a cycloalkyl, an alkenyl, an aralkyl or an aryl group, each of which may have a substituent; and two of R18d to R18f may connect together to form a ring. As the ring resulting from the connection of two of R18d to R18f, 3-to 8-membered ones are, for example, mentioned. Specific cyclic groups include cyclopropane, cyclopentane, cyclohexane, tetramethylene oxide, pentamethylene oxide, hexamethylene oxide, furan, pyran, dioxonol, 1,3-dioxolane, etc. R01 and R02 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group all of which may be substituted with one of the substituents enumerated above.
- Preferable examples include the ether or ester group of a tertiary alkyl group such as t-butyl, t-amyl, 1-alkyl-1-cyclohexyl, 2-alkyl-2-adamantyl, 2-adamantyl-2-propyl, 2-(4-methylcyclohexyl)-2-propyl, etc., the acetal or acetal ester group of 1-alkoxy-1-ethoxy, tetrahydropyranyl, etc., a t-alkylcarbonate group, a t-alkylcarbonylmethoxy group, etc. More preferable examples are the acetal groups of a 1-alkoxy-1-ethoxy group a tetrahydropyranyl group, etc.
- In the case of an acetal group, the resin is actively decomposed by acid. Accordingly, due to the expanded range of selection for the acid-generating compound to be jointly used, the resin is advantageous as regard to sensitivity enhancement, the property shift occurring in the period between exposure and post-baking, etc. Particularly preferable acetal groups are those containing the alkoxy group derived from the aforementioned perfluoroalkyl group as the 1-alkoxy component of the acetal. With such a compound, the transmittance of short wavelength rays (for example, the 157 nm light from an F2 excimer laser) can be further raised.
-
-
- Repeating unit (3) is one that is inactive to the action of acid and free of any alkali-soluble group; this unit has no such a group that is decomposed by acid to exhibit alkali-solubility as was explained hereinabove. To be inactive to the action of acid means that no chemical reaction results by the action of acid. This repeating unit is preferably selected from the group consisting of (meth) acrylic acid esters, (meth)acrylonitrile, and styrene that may contain an alkyl, alkoxy, acyloxy or haloalkyl group, or a chlorine, bromide or iodine atom as a substituent.
- To make sure, as the alkali-soluble group that repeating unit (3) does not contain, those, for example, having a pKa value not exceeding 11 are mentioned such as a phenolic hydroxide group, active methylene group, imide group, carboxyl group, sulfonic acid group, sulfinic acid group, etc.
- The monomer usable as repeating unit (3) includes, for example, those shown below. That is, such examples are compounds having one addition-polymerizable unsaturated bond chosen from, for example, acrylic acid esters, acrylamide derivatives, methacrylic acid esters, methacrylamide derivatives, allyl compounds, vinyl ethers, vinyl esters, styrene derivatives, crotonic acid esters, etc. except those defined above.
- Specific examples include the following. Acrylic acid esters such as, for example, alkyl (the number of the carbon atoms in the alkyl group being preferably 1 to 10) acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) and aryl acrylates (for example, phenyl acrylate, etc.);
methacrylic acid esters such as, for example, alkyl (the number' of the carbon atoms in the alkyl group being preferably 1 to 10) methacrylates (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amylmethacrylate, hexylmethacrylate, cyclohexylmethacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofur furyl methacrylate, etc.), and aryl methacrylates (for example, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.);
acrylamide derivatives such as acrylamide and N-alkylacrylamides (the alkyl group preferably having 1 to 10 carbon atoms, specifically including, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, benzyl, hydroxyethyl, etc.), N-arylacrylamide (the aryl group being, for example, phenyl, tolyl, nitrophenyl, naphthyl, cyanophenyl, hydroxyphenyl, carboxyphenyl, etc.), N,N-dialkylacrylamides (the alkyl group preferably having 1 to 10 carbon atoms, including, for example, methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl, etc.), N, N-diarylacrylamides (the aryl group being, for example phenyl, etc.), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide and N-2-acetamidoethyl-N-acetylacrylamide, etc.;
methacrylamides such as methacrylamide and N-alkylmethacrylamides (the alkyl group preferably having 1 to 10 carbon atoms, specifically including, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl, etc.), N-arylmethacrylamides (the aryl group being, for example, phenyl, etc.), N,N-dialkylmethacrylamides (the alkyl group including, for example, methyl, ethyl, propyl, butyl, etc.), N, N-diarylmethacrylamides (the aryl group being, for example, phenyl, etc.), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, etc.; allyl compounds such as allyl esters (including, for example, allyl acetate, allyl capronate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, etc.;
vinyl ethers such as, for example, alkyl vinyl ethers (including, for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ethere, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether,etc.), vinyl aryl ethers such as, for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.;
vinyl esters such as, for example, vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethylacetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl β-phenylbutyrate, vinylcyclohexylcarboxylate,vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.;
styrene derivatives such as, for example, styrene and alkylstyrenes (including, for example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrenes (including, for example, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogenated styrenes (including, for example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), carboxystyrenes and vinylnaphthalene;
crotonic acid esters such as, for example, alkyl crotonates (including, for example, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); dialkyl itaconates (including, for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of maleic acid or fumaric acid (including, for example, dimethyl maleate, dibutyl maleate, etc.), etc. In addition to these, any addition-polymerizable unsaturated compound that is copolymerizable may be used in general. - Repeating unit (3) is inactive to the action of acid, free of any alkali-soluble group, and preferably contains at least one fluorine atom.
- As this repeating unit (3), one can mention α-trifluoroacrylic acid esters, the fluorine-containing alkyl esters of (meth)acrylic acid, the benzenesulfonic acid esters of vinyl phenol that contain a fluorine atom or a fluorine-substituted alkyl group (exemplified by trifluoromethyl group) as substituent, and the repeating units represented by the general formula (IV') as defined in the appended Claim 4.
- The ester moiety of α-trifluoroacrylic acid esters consists of an alkyl group that contains preferably 1 to 20 carbon atoms and is of straight chain, branched chain or cyclic structure. But more preferably, the ester moiety consists of a straight chain, branched chain, or cyclic alkyl group containing 1 to 10 carbon atoms or a cyclic alkyl group containing 6 to 14 carbon atoms.
- The ester moiety of the fluorine-containing alkyl ester of (meth)acrylic acid consists of an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom and which is of straight chain, branched chain or cyclic structure with 1 to 20 carbon atoms. More preferably, the ester moiety is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom and which is of straight chain, branched chain or cyclic structure with 1 to 10 carbon atoms, or a cyclic alkyl group of 6 to 14 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.
- The number of the fluorine atoms usually lies in the range of from 1 to 38, and preferably from 2 to 19. As the fluorine-containing alkyl group, those that have no fluorine atom on the carbon atom bonded to the ester group are preferred.
- The definitions and specific examples of R5, R6, R7 and R50 to R55 in formula (IV') are the same as those of the corresponding groups in formula (I).
- R60 represents an alkyl group, an alkylcarbonyl group, a monocyclic or polycyclic cycloalkyl group, a monocyclic or polycyclic cycloalkylcarbonyl group, an alkenyl group, an alkenylcarbonyl group, an aralkyl group, an aralkylcarbonyl group, an aryl group or an arylcarbonyl group. To the alkyl, cycloalkyl, alkenyl, aralkyl, and aryl moieties of these groups, these that have been explained as the substituents in formulae (I) and (II) can be applied. As the group represented by R60, those in which at least one hydrogen atom is substituted with a fluorine atom are preferred.
- In the following, specific examples of repeating unit (3) are enumerated, but the scope of the invention is not limited by them. :
CF3CH2OCO(CH3)C=CH2
CF3CF3CH2OCO(CH3)C=CH2
F(CF2)4CH2CH2OCO(CH3)C=CH2
F(CF2)4CH2CH(OH)CH2OCO(CH3)C=CH2
F(CF2)6CH2CH2OCO(CH3)C=CH2
F(CF2)6CH2CH(OH)CH2OCO(CH3)C=CH2
F(CF2)8CH2CH2OCO(CH3)C=CH2
F(CF2)9CH2CH(OH)CH2OCO(CH3)C=CH2
F(CF2)10CH2CH2OCO(CH3)C=CH2
CF3CF(CF2)2CH2CH2OCO(CH3)C=CH2
CF3CF(CF2)2CH2CH(OH)CH2OCO(CH3)C=CH2
CF3CF(CF2)4CH2CH2OCO(CH3)C=CH2
CF3CF(CF2)4CH2CH(OH)CH2OCO(CH3)C=CH2
CF3CF(CF2)6CH2CH2OCO(CH3)C=CH2
CF3CF(CF2)6CH2CH(OH)CH2OCO(CH3)C=CH2
H(CF2)2CH2OCO(CH3)C=CH2
H(CF2)4CH2OCO(CH3)C=CH2
H(CF2)6CH2OCO(CH3)C=CH2
H(CF2)8CH2OCO(CH3)C=CH2
(CF3)2CHOCO(CH3)C=CH2
CF3CHFCF2CH2OCO(CH3)C=CH2
CF3CH2OCOCH=CH2
CF3CF3CH2OCOCH=CH2
F(CF2)4CH2CH2OCOCH=CH2
F(CF2)4CH2CH(OH)CH2OCOCH=CH2
F(CF2)6CH2CH2OCOCH=CH2
F(CF2)6CH2CH(OH)CH2OCOCH=CH2
F(CF2)9CH2CH2OCOCH=CH2
F(CF2)8CH2CH(OH)CH2OCOCH=CH2
F(CF2)10CH2CH2OCOCH=CH2
CF3CF(CF2)2CH2CH2OCOCH=CH2
CF3CF(CF2)2CH2CH(OH)CH2OCOCH=C
CF3CF(CF2)4CH2CH2OCOCH=CH2
CF3CF(CF2)4CH2CH(OH)CH2OCOCH=CH2
CF3CF(CF2)6CH2CH2OCOCH=CH2
CF3CF(CF2)6CH2CH(OH)CH2OCOCH=CH2
H(CF2)2CH2OCOCH=CH2
H(CF2)4CH2OCOCH=CH2
H(CF2)6CH2OCOCH=CH2
H(CF2)8CH2OCO(CH3)C=CH2
(CF3)2CHOCOCH=CH2
CF3CHFCF2CH2OCOCH=CH2
CH3OCO(CF3)C=CH2
CH3CH2OCO(CF3)C=CH2
CH3CH2CH2OCO(CF3)C=CH2
(CH3)2CHOCO(CF3)C=CH2
(CH3)2CHCH2OCO(CF3)C=CH2
CH3CH2CH2CH2OCO(CF3)C=CH2
C6H5CH=CH2
C6H4FCH=CH2
- The content of the repeating unit (1) represented by general formula (I) is usually 30 to 85 mol%, preferably 40 to 80 mol%, and still more preferably 50 to 70 mol% in resin (A).
- The content of the repeating unit (2) is usually 10 to 50 mol%, preferably 20 to 40 mol%, and still more preferably 25 to 35 mol% in resin (A).
- The content of the repeating unit (3) is usually 2 to 40 mol%, preferably 3 to 30 mol%, and still more preferably 5 to 20 mol% in resin (A).
- Resin (A) of the invention can contain, in addition to the repeating units cited above, another polymerizable monomer as a copolymerization component for the purpose of further improving various properties of the positive-type resist of the invention.
- Each repeating structural unit shown by the specific examples enumerated hereinabove may consist of single species or plural species used as mixtures.
- A preferable range of the molecular weight of resin (A) of the invention comprising the repeating units enumerated hereinabove is from 1, 000 to 200, 000, and more preferably from 3, 000 to 20,000 in terms of weight-average value for practical use. The molecular weight distribution lies in the range of 1 to 10, preferably 1 to 3, and more preferably 1 to 2 for practical use. Resins having a narrower molecular weight distribution excel in resolution, give rise to smooth resist configuration with smoother side walls of the resist pattern, and excel in the roughness characateristics. Based on the total solid content of the composition, resin (A) of the invention is used at a content of 50 to 99.5% by weight, preferably 60 to 98% by weight, and more preferably 65 to 95% by weight.
- Further, it is desirable to incorporate resin (A') that contains the above-cited repeating units (1) and (2) and decomposes by the action of acid to enhance the solubility in an alkali developer from the viewpoint of development defect reduction.
- The molecular weight of resin (A') is substantially the same as that of resin (A).
- Resin (A') is usually used in a content of from 2 to 30 % by weight, preferably 5 to 20% by weight, and more preferably 10 to 15% by weight relative to resin (A).
- The compound which generates an acid upon irradiation with one of an actinic ray and a radiation can be suitably selected from photo-initiators for cationic photo-polymerization, photo-initiators for radical photo-polymerization, photodecolouring agents for dyes, photodiscolouring agents and compounds which generate an acid upon irradiation with the known kinds of light now in practical use for in micro-resist fabrication etc., (including UV light of 400 to 200 nm wavelength, deep UV light, particularly preferably the g-line, h-line and i-line and KrF excimer laser light), the ArF excimer laser light, the F2 excimer laser light, electron beam, X-ray, molecular beam or ion beam. Further, mixtures of these compounds may also be appropriately used.
- Still other compounds that generate an acid upon irradiation with one of an actinic ray and a radiation include the onium salts such as the diazonium salts described in, for example, S. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T. S. Bal et al, Polymer, 21, 423 (1980), etc., the ammonium salts described in
US Patent Nos. 4,069,055 ,4,069,056 , andRe 27,992 , Japanese Patent Laid-Open No.140140/1991 US Patent Nos. 4,069,055 and4,069 ,056 , etc., the iodonium salts described in J. V. Crivello et al., Macromolecules, 10 (6) 1307 (1977), Chem. & Eng. News, Nov. 28, p. 31 (1988), European Patent Nos.104,143 339,049 410,201 150848/1990 296514/1990 370, 693 161, 811 410, 201 339, 049 233, 567 297, 443 297,442 US Patent Nos. 4,933,377 ,3,902,114 ,4,760,013 ,4,734,444 , and2,833,827 , German Patent Nos.2,904,626 ,3,604,580 and3,604,581 , etc., the selenonium salts described in J. V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. V. Crivello et al., Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), etc., the arsonium salts described in C. S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo, Oct. (1988), etc., etc.; the organic halogen compounds described inUS Patent No. 3, 905, 815 , Japanese Patent Publication No.4605/1971 36281/1973 32070/1980 239736/1985 169835/1986 169837/1986 58241/1987 212401/1987 70243/1988 298339/1988 161445/1990 0290,750 ,046,083 156,535 271,851 0,388,343 ,US Patent Nos. 3,901,710 and4,181,531 , Japanese Patent Laid-Open Nos.198538/1985 133022/1988 0199,672 ,84515 044,115 618,564 0101,122 ,US Patent Nos. 4, 371, 605 , and4,431,774 , Japanese Patent Laid-Open Nos.18143/1989 245756/1990 140109/1991 166544/1986 - Furthermore, compounds in which these groups or compounds capable of generating an acid upon irradiation with these actinic rays or radiations are introduced in the main chain or a side chain of a polymer, exemplified by those described in M. E. Woodhouse et al., J. Am. Chem. Soc., 104, 5586 (1982), S. P. Pappas et al., J. Imaging Sci., 30 (5), 218 (1986), S. Kondo et al., Makromol. Chem., Rapid Commun., 9, 625 (1988), Y. Yamada et al, Makromol. Chem., 152, 153, 163 (1972), J. V. Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979),
US Patent No. 3,849,137 , German Patent No.3, 914, 407 , Japanese Patent Laid-Open Nos.26653/1988 164824/1980 69263/1987 146038/1988 163452/1988 153853/1987 146029/1988 - Moreover, compounds which generate an acid by the action of light described in V. N. R. Pillai; Synthesis, (1), 1 (1980), A. Abad et al., Tetrahedron Lett., (47) 4555 (1971), D. H. R. Barton et al., J. Chem. Soc., (C), 329 (1970),
US Patent No. 3,779,778 , European Patent No.126,712 - Of the compounds which generate an acid upon irradiation with one of an actinic light and a radiation, those which are particularly used effectively will be described below.
- (1) Oxazole derivatives represented by the following general formula (PAG1) or S-triazine derivatives represented by general formula (PAG2), each being substituted with a trihalomethyl group.
- In the formulae, R201 is a substituted or unsubstituted aryl or alkenyl group, R202 is a substituted or unsubstituted aryl, alkenyl or alkyl group, or -CY3, where Y is a chlorine or bromine atom.
-
-
- In the formulae, Ar1 and Ar2 each independently represent a substituted or unsubstituted aryl group. As preferable substituents, one can mention an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.
- R203, R204, and R205 each independently represent a substituted or unsubstituted alkyl or aryl group, and preferably an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms or a substituted derivative of the two. Preferable substituents for the aryl group include an alkoxy group of 1 to 8 carbon atoms, an alkyl group of 1 to 8 carbon atoms, a cycloalkyl group, a nitro group, a carboxyl group, a mercapto group, a hydroxy group and a halogen atom. And preferred substituents for the alkyl group include an alkoxy, carboxyl or alkoxycarbonyl group of 1 to 8 carbon atoms.
- Z- represents an anion, specifically including the anions of an alkylsulfonic acid, cycloalkylsulfonic acid, perfluoroalkylsulfonic acid each of which may have a substituent, an arylsulfonic acid (exemplified by benzenesulfonic acid, naphthalenesulfonic acid and anthracenesulfonic acid each of which may have a substituent).
- Two of R203, R204 and R205 may connect together via a single bond thereof or a substituent. And, Ar1 and Ar2 may connect together via a single bond thereof or a substituent.
-
- The above-mentioned onium salts represented by general formulae (PAG3) and (PAG4) are known in the art and can be synthesized, for example, by the methods described in J. W. Knapczyk et al., J. Am. Chem. Soc., 91, 145 (1969), A. L. Maycok et al., J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bull. Soc. Chem. Belg., 73, 546, (1964), H. M. Leicester, J. Am. Chem. Soc., 51, 3587 (1929), J. V. Crivello et al., J. Polym. Chem. Ed., 18, 2677 (1980),
US Patent Nos. 2,807,648 and4,247,473 , Japanese Patent Laid-Open No.101331/1978 -
- In the formulae, Ar3 and Ar4 each independently represent a substituted or unsubstituted aryl group, R206 represents a substituted or unsubstitutedalkyl or aryl group, and A represents a substituted or unsubstituted alkylene, alkenylene or arylene group.
-
-
- Here, R represents an alkyl group of straight chain, branched chain or cyclic structure, or an aryl group that may be substituted.
-
-
- In the formula, R207 represents a substituted or unsubstituted alkyl, cycloalkyl, aryl or aralkyl group; R208 and R209 each represent a substituted or unsubstituted alkyl, cycloalkyl, aryl, aralkyl, cyano or acyl group; R208 and R209 may combine together to form a carbocyclic ring or a heterocycylic ring including an oxygen, nitrogen or sulfur atom.
-
- Among the photo-acid generators enumerated above, those represented by formulae (PAG3) to (PAG8) and capable of generating an organic sulfonic acid are preferred. In particular, such photo-acid generators that generate either a benzenesulfonic acid having a fluorine atom or a fluorine-substituted alkyl group as a substituent or a fluorine-containing alkylsulfonic acid are preferred. Nonaflate, pentafluorobenzenesulfonate and 3,5-bis(trifluoromethyl)benzenesulfonate are still more preferred.
- The added amount of the compound in (B) of the invention that generates an acid upon irradiation with one of an actinic ray or a radiation usually lies in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably 1 to 7% by weight based on the total solid content of the composition of the invention. These compounds may be used individually or in combination of two or more thereof.
- The composition of the invention is dissolved in a solvent which can dissolve each ingredient cited above and coated on a substrate. Preferable solvents used for such purpose include 1-methoxy-2-propanol acetate, 1-methoxy-2-propanol, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropinonate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc. Among them, 1-methoxy-2-propanol acetate and 1-methoxy-2-propanol are particularly preferred. These solvents may be used individually or as a mixture of two or more thereof.
- In the present invention, the amount of the components other than the solvent (total solid content) is usually 3 to 30wt%, preferably 5 to 25wt% based on content of the solvent.
- The positive resist composition of the invention can be incorporated with a surfactant containing at least one of a group consisting of a fluorine atom and a silicon atom. More specifically, the positive resist composition of the invention can contain one or more compounds selected from the group consisting of fluorine-containing surfactants, silicone-based surfactants and those containing both of fluorine and silicon atoms. The incorporation of the surfactant containing at least one of a group consisting of a fluorine atom and a silicon atom acts to effectively suppress the generation of development defect and improve coating performance.
- As such surfactants, those set forth, for example, in the following patents can be used. Japanese Patent Laid-Open Nos.
36,663/1987 226,746/1986 226,745/1986 170,950/1987 34,540/1988 230,165/1995 62,834/1996 54,432/1997 5,988/1997 USP Nos. 5,405,720 ,5,360,692 ,5,529,881 ,5,296,330 ,5,436,098 ,5,576,143 ,5,296,143 ,5,294,511 and5,824,451 . Moreover, the following commercially available surfactants can be used as they are. - As such commercially available surfactants, fluorine-containing or silicone-based surfactants such as, for example, Eftop EF301, EF303 and EF352 (all manufactured by Shin-Akita Kasei K. K.), Florad FC430 and 431 (both manufactured by Sumitomo 3M, Inc.), Megafac F171, F173, F176, F189 and R08 (all manufactured by Dainippon Ink and Chemicals, Inc.), Asahi-GardAG710, Surflon S-382, SC101, 102, 103, 104, 105 and 106, (all manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Industries, Inc.), etc. can be cited. Further, a polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.
- The incorporated amount of the surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight on the basis of the solid content in the composition of the invention. These surfactants may be used individually or in combination of two or more thereof.
- The composition of the invention is preferably incorporated with an acid diffusion-suppressing agent in order to prevent the performance shift caused not only by the time elapsed after the irradiation with an actinic ray or a radiation till post-baking (T-top shape formation, sensitivity fluctuation; patterned line width fluctuation, etc.), but also by the time elapse after coating, and further to suppress an excessive diffusion of acid during post-baking (which leads to the deterioration of pattern resolution). The acid diffusion-suppressing agent usually comprises an organic basic compound such as, for example, those containing a basic nitrogen, and a compound whose conjugated acid has a pKa value not less than 4 is preferably used.
-
- In the formulae, R250, R251 and R252, which may be the same or different, each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Here, R251 and R252 may connect together to form a ring.
- R253, R254, R255 and R256, which may be the same or different, each represent an alkyl group having 1 to 6 carbon atoms.
- More preferable compounds are nitrogen-containing basic compounds having two or more nitrogen atoms each lying in different chemical environments within a single molecule. Particularly preferable compounds are those containing both of a substituted or unsubstituted amino group and a cyclic structure including a nitrogen atom, or those containing an alkylamino group.
- Specific examples of preferable compounds include substituted or unsubstituted guanidines, substituted or unsubstituted aminopyridines, substituted or unsubstituted aminoalkylpyridines, substituted or unsubstituted aminopyrrolidines, substituted or unsubstituted indazoles, imidazole, substituted or unsubstituted pyrazoles, substituted or unsubstituted pyrazines, substituted or unsubstituted pyrimidines,substituted or unsubstituted purines,substituted or unsubstituted imidazolines, substituted or unsubstituted pyrazolines, substituted or unsubstituted piperazines, substituted or unsubstituted aminomorpholines, substituted or unsubstituted aminoalkylmorpholine, etc. Preferable substituents include an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxy group, a cyano group, etc.
- Particularly preferable compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperadine, N-(2-aminoethyl)piperadine, N-(2-aminoethyl)piperidine, 9-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1-(2-aminoethyl)pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2-(aminomethyl)-5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-(2-aminoethyl)morpholine, etc. However, the invention is not restricted to those enumerated compounds.
- These nitrogen-containing basic compounds can be used individually or in combination of two or more thereof.
- The use ratio of the acid-generating agent and the organic basic compound in the composition should preferably lie in the range of 2.5 to 300 in the molar ratio of (acid-generating agent) / (organic basic compound). In the case where this molar ratio is below 2.5, the sensitivity becomes low and the pattern resolution sometimes deteriorates; while, with a molar ratio over 300, not only resist patterns tend to fatten, resulting in resolution deterioration when the time after exposure till post-baking elapses too long, but also the pattern resolution sometimes deteriorates. The molar ratio of (acid-generator)/(organic basic compound) is preferably 5.0 to 200, and more preferably 7.0 to 150.
- In the manufacture of high precision LSI's, pattern formation in a resist film is performed by first coating the positive resist composition of the invention on a substrate (examples: a transparent substrate such as a silicon/silicon dioxide film, a glass substrate, an ITO plate, etc.), then conducting irradiation of the coating by means of an actinic light or radiation exposing apparatus, and thereafter conducting post-baking, developing, rinsing and drying. Via these procedures, a good-quality resist pattern can be formed.
- As the developer for the positive-type resist of the invention, one can use an aqueous solution of an alkali compound including inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, etc., and organic ones such as primary amines exemplified by ethylamine, n-propylamine, etc. , secondary amines exemplified by diethylamine, di-n-butylamine, etc., tertiary amines exemplified by triethylamine, methyldiethylamine, etc., alcohol amines exemplified by dimethylethanolamine, triethanolamine, etc., quaternary ammonium salts exemplified by tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc., cyclic amines exemplified by pyrole, piperidine, etc. and the like. The aqueous alkali solution enumerated above can further contain an alcohol such as isopropyl alcohol, etc. and a surfactant such as nonionic one each at an appropriate amount.
- Among the developers mentioned above, quaternary ammonium salts are preferred, and tetramethylammonium hydroxide and choline are still more preferred.
- In the following, the invention is explainedmore in detail with reference to Examples, by which, however, the content of the invention is not limited at all.
- Into 60 ml of 1-methoxy-2-proanol were dissolved 18.9 g(0.07 mol) of 9-[bis(trifluoromethyl)-hydroxymethyl]styrene, 3.52 g (0.02 mol) of 4-t-butoxystyrene, 1.04 g (0.01 mol) of styrene. To the resulting solution, 0.25 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd. with a trade Name of V-65) was added as a polymerization initiator. This solution was added dropwise to 10 ml of 1-methoxy-2-propanol heated to 70°C over the period of 2 hours under stirring along with the injection of nitrogen gas. After the completion of addition, stirring was continued for 4 hours. Thereafter, the reaction solution was thrown into 1 liter of a methanol/ion-exchanged water (1/1) mixture under vigorous stirring. The deposited resin was washed with ion-exchanged water, filtered and dried in vacuo to give 16.1 g of a white resin. By an NMR measurement, it was confirmed that this resin has the structure of P-1 (consisting of the repeating units listed in Table 1 in molar ratios of 70/20/10 from the leftmost repeating unit). A GPC measurement proved that the weight averagemolecularweight of the resin (calculated in terms of polystyrene) was 15,000.
- Each of the resins shown in Table 1 was synthesized in a similar manner.
Table 1 Resin (A) Structure Molecular Weight P-1 15000 P-2 23000 P-3 29000 P-4 26000 P-5 27000 P-6 37000 P-7 19000 P-8* 30000 P-9 25000 P-10 21000 P-11* 10000 P-12 19000 B-1 16000 B-2 21000 B-3 23000 C-1 17000 *For reference and not within the scope of resing (A) - As Examples 1 to 6, to 1.36 g of each of resins (P-1) to (P-6) shown in Table 1 above, 0.02 g of the nonaflate salt of triphenylsulfonium (PAG4-3) and 0.02 g of an imidosulfonate compound (PAG6-19) were added; the mixture was dissolved in 8.5 g of 1-methoxy-2-propanol acetate; and, to the solution, 0.005 g of dicyclohexylmethylamine and 0.01 g of Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) as a fluorine-containing surfactant were added to give a resist composition of the invention. As Examples 7 to 12 (Examples 8 and 11 being for reference and not within the scope of invention), to 1.36 g of each of resins (P-7) to (P-12), 0.04 g of the nonaflate salt of triphenylsulfonium (PAG4-3) was added; the mixture was dissolved in 8.5 g of 1-methoxy-2-propanol acetate; and to the solution, 0.005 g of dicyclohexylmethylamine and 0.01 g of Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) as a fluorine-containing surfactant were added to give a resist composition of the invention.
- As Example 13, a resist composition was prepared in a similar manner as in Example 1 except that, instead of 1.36 g of (P-1), 1.2 g of (P-1) and 0.16 g of a complementary resin (B-1) were used.
- As (Reference) Example 14, a resist composition was prepared in a similar manner as in (Reference) Example 8 except that instead of 1.36 g of (P-8), 1.2 g of (P-8) and 0.16 g of a complementary resin (B-1) were used.
- As Example 15, a resist composition was prepared in a similar manner as in Example 5 except that instead of 1.36 g of (P-5), 1.2 g of (P-5) and 0.16 g of a complementary resin (B-3) were used.
- Further, as Comparative Example 1, a resist composition was prepared in a similar manner as in Example 1 except that the resin was changed to (C-1) shown in Table 1.
- After filtered through a Teflon filter of 0.1 µm aperture size, each resist solution prepared above was coated, with use of a spin coater, on a silicon wafer that had been subjected to a hexamethyldisilazane treatment, and dried on a vacuum contact type-hot plate kept at 110°C for 90 sec to give a 0.3 µm thick resist film. The resist film thus obtained was subjected to an image exposure with a KrF excimer stepper (FPA-3000EX5, a product of Canon, Inc.), followedbypost-baking at 110°C for 90 sec. Thereafter, the resist film was developed with a 0.262 N TMAH aqueous solution to give a L/S pattern of 0.15 µm rule.
[Surface Roughness] The degree of roughness at the surface of the line area in the 0.15 µm rule line-and-space pattern was examined with an SEM for visual evaluation. The samples in which substantially no roughness (unevenness) was observed were evaluated as A, those in which roughness was faintly recognized were evaluated as B, and those in which roughness was clearly recognized were evaluated as C.
[Number of Particles and Particle Increment after Storage Time Passage] For each resist composition solution (coating solution) prepared above, the number of particles therein was counted just after the preparation of the solution (Initial Particle Number) and that after one-week storage at 4°C (Particle Number after Storage Time Passage) with use of a particle counter manufactured by Rion K. K. In addition to the initial particle number, the: particle increment was calculated by (Particle Number After Time Passage) - (Initial Particle Number) for evaluation. The number of particles with a size of 0.3 µm or larger present in one ml of the resist composition solution was counted.
[Number of Development Defect] For each resist pattern prepared according to the procedures described above, the number of development defect was measured with use of a KLA-2112 inspector manufactured by KLA-Tencor Corp. The primary data obtained was regarded as the number of development defect. - The results are shown in Table 2.
Table 2 Resin (A) Jointly Used Resin Surface Roughness Number of Particles in Fluid Development Defect Initial Value Increment Example 1 P-1 None A 36 57 36 2 P-2 None A 47 73 38 3 P-3 None B 29 51 38 4 P-4 None A 38 62 38 5 P-5 None A 46 63 49 6 P-6 None A 37 74 51 7 P-7 None B 47 57 38 8* P-8 None A 34 72 45 9 P-9 None A 49 83 39 10 P-10 None B 29 79 45 11* P-11 None A 26 57 42 12 P-12 None A 27 61 49 13 P-1 B-1 B 48 81 22 14* P-8 B-2 A 46 72 23 15 P-5 B-3 B 40 74 24 Comparative Example 1 C-1 None C 110 187 55 * Reference Example outside the scope of invention - It has been confirmed that, according to the invention, the particle number in the resist fluid is desirably small immediately after preparation as well as after storage, and the surface roughness was excellent.
- Into 60 ml of 1-methoxy-2-propanol were dissolved 18.9 g (0.07mol) of 4-[bis(trifluoromethyl)-hydroxymethyl]styrene, 3.52 g (0.02 mol) of 4-t-butoxystyrene, 1.94 g (0.01 mol) of pentafluorostyrene. To the resulting solution, 0.25 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was added as a polymerization initiator. This solution was added dropwise to 10 ml of 1-methoxy-2-propanol heated to 70°C over the period of 2 hours under stirring along with the injection of nitrogen gas. After the completion of addition, stirring was continued for 4 hours. Thereafter, the reaction solution was thrown into 1 liter of a methanol/ion-exchanged water (1/1) mixture under vigorous stirring. The deposited resin was washed with ion-exchanged water, filtered and dried in vacuo to give 16.1 g of a white resin. By NMR measurement, it was confirmed that this resin has the structure of P-21 (consisting of the repeating units listed in Table 1 in molar ratios of 70/20/10 starting from the leftmost repeating unit). A GPC measurement proved that the weight average molecular weight of the resin (calculated in terms of polystyrene) was 19,000.
- Each of the resins shown in Table 3 was synthesized in a similar manner.
Table 3 (In Table 3, the asterisk "*" denotes resins which are for reference and not within the scope of resin (A)) Resin (A) Structure Molecular weight P-21 19000 P-22 26000 P-23 19000 P-24 28000 P-25 23000 P-26* 31000 P-27 16000 P-28* 26000 P-29* 20000 P-30 13000 P-31* 17000 P-32 18000 - To 1.36 g of each of resins (P-21) to (P-26) shown in Table 3 above, 0. 02 g of the nonaflate salt of triphenylsulfonium (PAG4-3) and 0.02 g of an imidosulfonate compound (PAG6-19) were added; the mixture was dissolved in 8.5 g of 1-methoxy-2-propanol acetate; and, to the solution, 0.005 g of dicyclohexylmethylamine and 0.01 g of Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) as a fluorine-containing surfactant were added to give a resist composition of the invention. To 1. 36 g of each of resins (P-27) to (P-32), 0.04 g of the nonaflate salt of triphenylsulfonium (PAG4-3) was added; the mixture was dissolved in 8.5 g of 1-methoxy-2-propanol acetate. To the resulting solution, 0.005 g of dicyclohexylmethylamine and 0.01 g of Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) as a fluorine-containing surfactant were added to give a resist composition of the invention.
- As Comparative Example 2, a resist solution was prepared in a similar manner as in Example 21 except that the resin component described above was changed to a copolymer of 4-[bis(trifluoromethyl)-hydroxymethyl]styrene and t-butyl methacrylate (copolymerization molar ratio = 65/35, weight average molecular weight = 17000) (Resin C-2).
- As Comparative Example 3, a resist solution was prepared in a similar manner as in Example 21 except that the resin component described above was changed to a copolymer of 4-(hydroxymethyl)styrene, 4-(t-butoxy)sytrene and 2,2,2-trifluoromethyl methacrylate (copolymerization molar ratio = 40/40/20, weight average molecular weight = 18000) (Resin C-3).
- After filtered through a Teflon filter of 0.1 µm aperture size, each resist solution prepared above was coated, with use of a spin coater, on a silicon wafer that had been subjected to a hexamethyldisilazane treatment, and dried on a vacuum contact type-hot plate kept at 110°C for 90 sec to give a 0.3 µm thick resist film. The coated film was subjected to an image exposure with a KrF excimer stepper (FPA-3000EX5, a product of Canon, Inc.). Then, after post-baked at 110°C for 90 sec, the resist film was developed with a 0. 262 N TMAH aqueous solution to give a L/S pattern of 0.13 µm rule.
[Surface Roughness] The degree of roughness at the top surface of the line area in the 0.13 µm/0.13 µm line-and-space pattern was examined with an SEM for visual evaluation. The samples in which substantially no roughness (unevenness) was recognized were evaluated as A, those in which roughness was faintly recognized were evaluated as B, and those in which roughness was clearly recognized were evaluated as C.
[Scum] The space areas in the 0.13 µm/0.13 µm line-and-space pattern were examined with an SEM for visual evaluation. The samples in which substantially no scum was observed were evaluated as A, those in which scum was faintly observed were evaluated as B, and those in which scum was noticeably observed were evaluated as C. - The results are shown in Table 4.
Table 4 Resin Surface Roughness Scum Example 21 P-21 A A 22 P-22 A B 23 P-23 B A 24 P-24 A A 25 P-25 A B 26* P-26 A B 27 P-27 B A 28* P-28 A A 29* P-29 A A 30 P-30 B B 31* P-31 A B 32 P-32 A A Comparative Example 2 C-2 C C Comparative Example 3 C-3 C C * Reference Example outside the scope of invention - It was confirmed that the resist compositions comprising a fluorine atom-containing resin according to the invention are preferable giving little surface roughness and scum.
- Into 60 ml of 1-methoxy-2-propanol were dissolved 18.9 g (0.07 mol) of 4-[bis(trifluoromethyl)-hydroxymethyl]styrene, 3.52 g (0.02 mol) of 4-(t-butoxy)styrene, and 2. 36 g (0.01 mol) of 1,1-bis(trifuloromethyl)-ethyl acrylate. To the solution 0.25 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was added as a polymerization initiator. This solution was added dropwise to 10 ml of 1-methoxy-2-propanol heated to 70°C over the period of 2 hours under stirring along with the injection of nitrogen gas. After the completion of addition, stirring was continued for 4 hours. Thereafter, the reaction solution was thrown into 1 liter of a methanol/ion-exchanged water (1/1) mixture under vigorous stirring. The deposited resin was washed with ion-exchanged water, filtered and dried in vacuo to give 15.6 g of a white resin. By NMR measurement, it was confirmed that this resin has the molar composition of 70/20/10. A GPC measurement proved that the weight average molecular weight of the resin (calculated in terms of polystyrene) was 13,000.
- In a similar manner, the following resins of the invention were synthesized.
Structure Molecular Weight P-41 13000 P-42 25000 P-43 19000 P-44 26500 P-45 31000 P-46 9600 P-47 17900 P-48 35000 P-49 18000 P-50 22000 P-51 20000 P-52 11500 P-53 18000 P-54 21000 P-55 18000 P-56 20000 P-57 24000 P-58 17000 - To 1.36 g of each of resins (P-41) to (P-46) shown above, 0.02 g of the nonaflate salt of triphenylsulfonium (PAG4-3) and 0.02 g of an imidosulfonate compound (PAG6-19) were added; the mixture was dissolved in 8.5 g of 1-methoxy-2-propanol acetate. To the solution, 0.005 g of dicyclohexylmethylamine and 0.01 g of Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) as a fluorine-containing surfactant were added to give a resist composition of the invention. To 1.36 g of each of resins (P-47) to (P-58), 0.04 g of the nonaflate salt of triphenylsulfonium (PAG4-3) was added; the mixture was dissolved in 8.5 g of propylene glycol monomethyl ether acetate. To the resulting solution, 0.005 g of dicyclohexylmethylamine and 0.01 g of Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) as a fluorine-containing surfactant were added to give a resist composition of the invention.
- As Comparative Example 4, a resist composition was prepared as a KrF resist for comparison in a similar manner as in Example 41 except that the resin of the invention described above was changed to poly[(4-hydroxystyrene)-(4-t-butoxycarbonyloxystyrene)] (copolymerization molar ratio = 65/35, weight average molecular weight = 15000) was used.
- After filtered through a Teflon filter of 0.1 µm aperture size, each sample solution was coated on a calcium fluoride disk with use of a spin coater, and dried at 120°C for 5 min to give a 0.1 µm thick resist film. The absorption of the coated film was measured with an Acton CAMS-507 spectrometer, and the transmittance at 157 nm was calculated. The results are shown in Table 5.
Table 5 Resin of the Invention Transmittance at 157 nm (%) P-41 38 P-42 38 P-43 42 P-44 46 P-45 40 P-46 40 P-47 36 P-48 38 P-49 42 P-50 46 P-51 40 P-52 44 P-53 37 P-54 37 P-55 35 P-56 36 P-57 35 P-58 35 Comparative Example 4 (Acetal-based KrF resist) 18 - From the results in Table 5, it is seen that the measured transmittance of the coated film using the composition prepared according to the invention exceeds 35% for every sample, indicating that all the samples are sufficiently transparent at 157 nm.
- The surfactant used in each sample prepared for transmittance measurement described above was changed to the following surfactants, W-1 to W-4, to prepare resist compositions of the invention. The surfactants used are shown in Table 6.
- Each code represents the following surfactants.
W1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine-containing type)
W2: Megafac R08 (made by Dainippon Ink and Chemicals, Inc.) (fluorine-containing and silicon-based)
W3: Polysiloxane polymer KR-341 (made by Shin-Etsu Chemical Co., Ltd.)
W4: Polyoxyethylene nonyl phenyl ether - After filtered through a Teflon filter of 0.1 µm aperture size, each resist solution was coated, with use of a spin coater, on a silicon wafer that had been subjected to a hexamethyldisilazane treatment, and dried on a vacuum contact type-hot plate kept at 110°C for 90 sec to give a 0.3 µm thick resist film. The coated film was subjected to an image exposure with a KrF excimer stepper (FPA-3000EX5, a product of Canon, Inc.). Then, after post-baked at 110°C for 90 sec, the resist film was developed with a 0.262 N TMAH aqueous solution to give a L/S pattern of 0.15 µm rule.
- Development defect and coating performance were evaluated as follows.
[Number of Development Defect] For each resist pattern prepared according to the procedures described above, the number of development defect was measured with use of a KLA-2112 inspector manufactured by KLA-Tencor Corp. The primary data obtained was regarded as the number of development defect. - Each resist solution was coated on an 8-inch silicon wafer. Then, the same procedures for the preparation of the resist coating as described above were conducted to give a coated resist film for the measurement of the uniformity over the entire coated plane. With use of Lambda A manufactured by Dainippon Screen Mfg. Co., Ltd., the thickness of the coating was measured at 36 points evenly distributed along two wafer diameter directions running crosswise. The standard deviation of all the measured values was calculated. The samples in which the threefold of the standard deviation did not exceed 50 were evaluated as O, those in which the value was 50 or larger were evaluated as X.
- The results of performance evaluation are shown in Table 6.
Table 6 Resin (A) of the Invention Surfactant Used Development Defect Coating Performance P-41 W1 30 O P-42 W2 24 O P-43 W3 20 O P-44 W2 36 O P-45 W2 30 O P-46 W3 24 O P-47 W1 22 O P-48 W2 30 O P-49 W3 30 O P-50 W2 28 O P-51 W1 40 O P-52 W3 36 O P-53 W3 35 O P-54 W3 32 O P-55 W1 38 O P-56 W2 48 O P-57 W1 46 O P-58 W1 48 O P-41 None 2000 X P-41 W4 650 X - From the results in Table 6, it is seen that the composition of the invention that is incorporated with a surfactant containing at least one of a group consisting of a fluorine atom and a silicon atom is superior, compared to Comparative Examples in which no such surfactant is incorporated, as for coating performance and gives rise to far fewer development defects.
- By using resins of the invention, resist solutions were prepared in the same way as in the term of [Measurement of Transmittance]. After filtered through a Teflon filter of 0.1 µm aperture size, each resist solution prepared above was coated on a silicon wafer that had been subjected to a hexamethyldisilazane treatment with use of a spin coater, and dried on a vacuum contact type-hot plate kept at 110°C for 90 sec to give a 0.1 µm thick resist film. A 157 nm laser exposure-and-dissolution behavior analyzing apparatus, VUVES-4500 (manufactured by Lithotec Japan Corp.) was used for each of the resulting resist films to measure the dissolution contrast between the exposed and unexposed regions for 157 nm irradiation.
- The results are shown in Table 7.
Table 7 Resin of the Invention Dissolution Contrast (tanθ) P-41 6.0 P-42 6.4 P-43 6.8 P-44 6.4 P-45 6.0 P-46 6.4 P-47 6.4 P-48 6.0 P-49 6.1 P-50 6.1 P-51 6.0 P-52 6.5 P-53 6.2 P-54 5.8 P-55 5.9 P-56 6.1 P-57 6.0 P-58 6.0 Comparative Example 5 (Acetal-based KrF resist) 5.3 *1) *1) The value when the resist was exposed to the KrF excimer laser (248 nm). - From the results of Table 7, it is seen that the compositions of the invention exhibit a dissolution contrast equivalent to that of the resist of the comparative example that is practically used for the KrF excimer laser, and thus have an equivalent image forming capability.
- With use of a positive resist composition of the invention, one can further provide a positive resist composition with which surface roughness and storage stability are improved along with reduced development defect.
- Further, one can provide a positive resist composition with reduced surface roughness and scum owing to the use of specified fluorine atom-containing resins.
- Still further, with use of the positive resist composition of the invention, one can provide a positive resist composition that exhibits a sufficient transparency and a desirable image forming capability at a wavelength region as short as 157 nm, and that improves the coating performance and the development defect problem both of which are deteriorated by the use of a fluorine-containing resin.
Claims (7)
- A positive resist composition comprising:(A) a resin which decomposes by the action of acid to increase the solubility in an alkali developer, the resin comprising:a repeating unit (1) represented by the following general formula (I);a repeating unit (2) represented by the following general formula (II) that is copolymerizable with the repeating unit represented by the general formula (I) and has the function of decomposing by the action of acid to increase the solubility of the resin in an alkali developer; anda repeating unit (3) that is inactive to the action of acid and free of an alkali-soluble group; and(B) a compound capable of generating an acid upon irradiation with one of an actinic ray and a radiation:
- The positive resist composition according to Claim. 1, wherein the repeating unit (3) contains at least one fluorine atom.
- The positive resist composition according to Claim 1, wherein the repeating unit (3) is a repeating unit corresponding to a monomer selected from the group consisting of: a (meth) acrylic acid ester; a (meth) acrylonitrile; and a styrene that may contain an alkyl group, an alkoxy group, an acyloxy group, a haloalkyl group, a chlorine atom, a bromine atom or a iodine atom as a substituent.
- The positive resist composition according to Claim 2, wherein the repeating unit (3) is a repeating unit selected from the group consisting of: a repeating unit corresponding to an α-trifluoroacrylic acid ester; a repeating unit corresponding to a fluorine-containing alkyl ester of (meth)acrylic acid; a repeating unit corresponding to a vinylphenol ester of a benzene sulfonic acid containing one of a fluorine atom and a fluorine-substituted alkyl group; and a repeating unit represented by the following formula (IV'):
- The positive resist composition according to Claim 1, which further comprises a resin decomposing by the action of acid to increase the solubility in an alkali developer, the resin containing the repeating units (1) and (2).
- The positive resist composition according to Claim 1, which further comprises (D) a surfactant containing at least one of a fluorine atom and a silicon atom.
- The positive resist composition according to Claim 1, which further comprises a basic compound containing a nitrogen atom as (E) an inhibitor of acid diffusion.
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JP2001202240 | 2001-07-03 | ||
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JP3874061B2 (en) * | 1999-08-30 | 2007-01-31 | 信越化学工業株式会社 | Polymer compound, resist material, and pattern forming method |
US6461791B1 (en) * | 1999-10-13 | 2002-10-08 | Shin-Etsu Chemical Co., Ltd. | Polymers, chemical amplification resist compositions and patterning process |
US20020155376A1 (en) * | 2000-09-11 | 2002-10-24 | Kazuhiko Hashimoto | Positive resist composition |
JP4190167B2 (en) * | 2000-09-26 | 2008-12-03 | 富士フイルム株式会社 | Positive resist composition |
JP2002239678A (en) | 2001-02-08 | 2002-08-27 | Fukui Byora Co Ltd | Rivet feeder |
US6794109B2 (en) * | 2001-02-23 | 2004-09-21 | Massachusetts Institute Of Technology | Low abosorbing resists for 157 nm lithography |
US6610456B2 (en) * | 2001-02-26 | 2003-08-26 | International Business Machines Corporation | Fluorine-containing styrene acrylate copolymers and use thereof in lithographic photoresist compositions |
JP2002296781A (en) * | 2001-03-30 | 2002-10-09 | Sumitomo Chem Co Ltd | Resist composition |
JP4418605B2 (en) * | 2001-04-11 | 2010-02-17 | パナソニック株式会社 | Pattern forming material and pattern forming method |
JP4137408B2 (en) * | 2001-05-31 | 2008-08-20 | 富士フイルム株式会社 | Positive resist composition |
-
2002
- 2002-06-27 KR KR1020020036404A patent/KR100863984B1/en not_active IP Right Cessation
- 2002-07-01 EP EP02014079.4A patent/EP1273969B1/en not_active Expired - Fee Related
- 2002-07-01 TW TW091114501A patent/TWI269117B/en not_active IP Right Cessation
- 2002-07-02 US US10/187,291 patent/US6878502B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US20030134224A1 (en) | 2003-07-17 |
EP1273969A2 (en) | 2003-01-08 |
KR20030023461A (en) | 2003-03-19 |
US6878502B2 (en) | 2005-04-12 |
EP1273969A3 (en) | 2003-10-22 |
TWI269117B (en) | 2006-12-21 |
KR100863984B1 (en) | 2008-10-16 |
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